Headspace solid-phase microextraction (HS-SPME) has been used for determining sulphur compounds with low volatility in wines. With this technique, handling of samples is minimal so undesirable loses and reactions between compounds are prevented. Furthermore, this kind of extraction is fast and does not require any organic solvent. Under optimal conditions, the HS-SPME, using a new fibre coated with Stable Flex divinylbenzene-Carboxen-polydimethylsiloxane, makes possible the quantification of sixteen sulphur compounds with low volatility which may be present in wines. The limits of detection for the analytes studied ranged between 0.05 and 10 microg/l, and the recovery and repeatability found were acceptable. The method developed was successfully applied to determine the concentration of the target analytes in varietal wines from the Catalonian region (Spain) with some aromatic defects such as an odour of rubber, onion, rotten, unpleasant herbaceous, etc. The results show that the contents of the sulphur compounds studied in these wines are higher than in those without defects. This shows a relationship exists between the presence of sulphur compounds and the quality of the wine aroma.